Sylvania



Patented A r.' 1,-193 o UNITED STATES PATENT orrlcs LOUIS J. TROSTEL, OF BALTIMORE, MARYLAND, ASSIGNOR TO GENERAL REFRAC- TORIES COMPANY, OF PHILADELPHIA, PENNSYLVANIA, A CORPORATION OF PENN- SYLVAN IA REFRACTORY COMPOSITION AND PROCESS OF MAKING REFRACTORY ARTICLES THEREFROM 1T0 Drawing.

. This invention relates to a new and improved refractory composition and process for manufacturing same.

The process consists in adding to a body 5 mix of a mineral, a member having a very stable crystalline and chemical form at elevated temperatures. This member becomes a fractional part of the mix, but its incorporation enables the material to be wetted and shaped and thereafter dried and burned without either loss of shape, or material loss of volume, within the range of very high temperatures suchas are developed in industrial furnaces.

The object of the invention is to provide a brick or other molded article of the superrefractory class of highly aluminous content that will not continue to sufi'er appreciable volume'changes in service at temperatures at or above the temperatures employed in burning the brick in the usual course of manufacture.

Another object is to provide such brick by a method of manufacture which consists in introducing a suitable quantity of the mineral mullite, into a brick mix consisting of one or more of the hydrous oxide of aluminum minerals, diaspore, bauxite, or gibbsite,

which may be mixed together in the raw or calcined state, orboth states simultaneously.

Another object is to provide such brick by introducing a highly refractory mineral which because of inherent stable crystalline and chemical properties at elevated temperatures sufiers no appreciable change in volume and thus furnishes to the brick in general a rigid skeleton or crystalline framework on which the grains of the mineral diaspore, bauxite, or gibbsite, may coalesce or condense. This condensation of the diaspore, bauxite, or gibbsite ains proceeds with increasing intensity o temperature and with increasing number of exposures to elevated temperatures.

It is a well-known fact that these particular hydrous oxides of aluminum mentioned, that is the minerals diaspore, bauxite, and gibbsite, show an unusually high shrinkage upon heatin at elevated temperatures when 50 compared with the hydrous aluminum sili- Application filed March 30, 1927. Serial No. 179,720.

cates or ordinar fireclays, and that this extremely high firing shrinkage has prevented the more general use of these materials for refractory purposes- Phelps, in the Journal of the American Ceramic Society 10, 659 (1926), has shown from microscopic examination that the typical diaspore oolites for instance consist of comparatively large amorphous grains. around 1400 C., the rather large amorphous grains start crystallizing into a dense mass with an accompanying high shrinkage. This shrinkage was further verified by showing that there is an accompanying increase in specific gravity as the crystallization proceeds. The shrinkage due to the removal of'ehemically and mechanically contained water is neg igible by comparison.

the two oxides mentioned and the molecular chemical formula is accordingly given as Al O .2H O. Some small amount of acces- Upon heating repeatedly at The naturally occurring hydrous oxides of I sory fireclay will at times accompany these oxides as an impurity. Thespecific gravity of pure diaspore is 3.3 to 3.5. 'However it is not unusual practice to mine diaspore of a specific-gravity of 3.4, indicating the high purity of the mineral available for refractory purposes.

This conception of the hydrous oxideof aluminum will serve to distinguish them from ordinary firecla which is generally accepted as consisting 0 one or more of the hydrous aluminum silicates. The molecular chemical formula of fireclay is approximately Al O .2SiO .2H O, i. e that of kaolinite. The usual fireclays do not exhibit the property of extremel high firing shrinkage as do the minerals iaspore, bauxite and gibbsite, as the comparative porosities of typical sound commercial refractories made from the mineral diaspore on one hand and from the usual fireclays on the other hand will indicate, i. e. diaspore about, 30-35%, fireclay 1015%. This rather small firing shrinkage in fireclay is not a function of shrinkage of large amorphous rains to small crystalline grams as m, say 'aspore, but is due largely grain size. The introduction of the calcined portion is made for the purposes of attempting to control shrinkage in subsequent burning of the whole batch. The raw and calcined ortions of the batch are generally oun separately or-together, to the usual eness for firebrickmanufacture, tempered with water and then pressed into brick by hand molding or machines. Following this, these bricks are dried to remove mechanically contained moisture and burned at a temperature which causes further shrinkage.

It is impossible by the usual burning treat- I ment in practice to remove all shrinkage of brick made from the hydrous oxides" of aluminum.' It is further impractical to attempt to do so by increased temperature and time of burning alone, because of the fuel exnse, increased kiln repairs, lowered prouction and because of certain other undesirable reactions which would take place in i the brick.

It is further impractical to eliminate this shrinkage by the introduction of very large amounts of calcined dias ore for instance, because of the difliculties 1n molding, which causes an extremely poorly bonded brick so friable it will not stand handling. Further, the use of a large amount of calcined diaspore for instance, is no insurance against s rinkage, because the calcined diaspore still has some shrinkage in it, due to the fact that l the practicaltem erature of calcination is consisting o rarely high enou'g' to shrink the amorphous diaspore to its ultimate stable crystalline grain size. I

Accordingly, bricks made from the hydrous' oxides of aluminum continue to shrink when exposed to sufiiciently high temperatures in industrial furnaces, resulting at times in collapse of arches, spelling and slag penetration and attack of the brick.

I have found that small percentages of the mineral mullite ground to approximately the same screen size as the usual mix and added in pro er pro ortions into a brick mix fj'say iaspore, 'willproduce a burned brick of practically constant volume and that this brick of new composition will maintain a practically constant volume ovler a temperature range comparable with that which these brick will ordinarily be subjected toin industrial furnaces.

By mullite, I refer to either the naturally occuring mineral as found on the island of Mull as described by Thomas in the Quar. J our. Geol. Soc. 78,229 1922) and which has the molecular chemical ormula of 'is quite in excess ofthat of the ordinary aluminum silicates of the, kaolinite type.

Mullite accordingly shows no medical changes in expansion or contraction, over the working temperature range of most refractories, 1400-1700 0., and should make an ideal reenforcing medium in a refractory mix which suffers from change in she e or volume due to the type of shrinkage escribed as characteristic of the hydrous oxides of aluminum.

Its introduction therefore in small percentages into a mix of one of the hydrous oxides of aluminum, as diaspore, is to provide a very stable skeleton or crystalline framework, onto which the amorphous grains of diaspore may condense at kiln and furnace temperatures. The net effect is to produce a brick or other molded article of apparently and for all practical purposes of constant volume.

The mixture I have found most satisfactory for a brick made from the mineral diaspore for instance, which is the highest in alumina content of the hydrous oxides of alumina, is about 60 to of the crude mineral, 20 to 30% calcined diaspore and about 10% mullite.

While the above mixture is the preferred one, it is to be understood that the proportions and character of the ingredients may be changed. The proportions of the mullite for instance may be varied from 2 to 20%, depending upon the amount of calcined diaspore in the brick mix. I also anticipate the use of dumortierite as a source of mullite, and do not limit myself to the use of the natural mineral mullite, or such minerals as cyanite, andalusite and sillimanite.

Referring to the use of dumortierite, I have found that this material can be used as a possible source of mullite, providing that a cheap sgpply of the raw material becomes availa e.

It is .to be noted articularly, that the proc ess provides, pref erably, for the direct introduction into the batch mixture of mullite, as such, instead of a material which under the firing treatment of the batch will produce mulllte. Although the invention, in some aspects, is not to be considered as limited to the-use of mullite as such, i. e., either natural mullite or mullite obtained by the processin of such materials as cyanite, andalusite an sillimanite, there is a distinct advantage, as will be understood from the foregoing description, in employing this material initially instead ofdepending upon the treatment of the entire batch to produce it.

Among the advantages of using the artificial mullite in thebatch initially instead of depending upon the treatment of a batch con-. tainin a mullite forming mineral are:

1. C omplete conversion to mullite can be more efliciently and completely efiected by a separate heat treatment of the raw materials -(e. g. cyanite, andalusite and sillimanite) outside of the batch. When the .raw materials are dispersed as a fractional part of the batch, it is doubtful at times whether or not complete conversion occurs. This separate processing insures a more uniform and dependable material.

2. In the formation of mullite by heating, from oneof the group of sillimanite minerals, there is set free a molecule of silica which is .present as either free silica in one of its crystalline modifications, such as quartz, cristobalite and tridymite, or as silica glass. This free silica adds undesirable qualities to the batch in that it increases the spalling properties of the finished product, and decreases the load bearing properties at elevated tem ratures. By forming mullite outside of t e batch, the necessary purification processes can be made to insure a mullite of more constant purity.

3. The temperature necessary to convert sillimanite to mullite occasionally must be carried out to 1545 degrees centigrade. This isin excess of the temperature necessary to burn the rest of the batch. Fuel economy is therefore efiected by separately heating only the relatively small amount of sillimanite to 1545 degrees centigrade to form mullite, and then heatin the final batch to the usual temperature 0 only about 1400 centigrade.

It is found that mullite obtained from cyanite, andalusite and sillimanite is especially efiective.

It is to be understood that the invention the uses of this batch is in the manufacture more of the hydrous oxides of the aluminum minerals, since in some cases it may be desirable to use, for example, any two of the minerals to form the batch or any three of the minerals to form the batch, and appli' cant does not wish to be considered as claims mg a batch comprising but a single one of these materials.

Referrin to the shrinkage of the mass in the appen ed claims, it Wlll be understood that the use of the word mass is employed to mean the body containing the hydrous oxides of. aluminum and mullite as a whole.

What I claim is I 1.. A. batch mixture for forming refractory A bodies, containing a hydrous oxide of alu- .minum and suflic ent mullite to prevent the shrinkage of the mass during firing.

2. A batch mixture for forming refractory bodies containing a hydrousoxide of aluminum and 2 to 20% mullite to preventv shrinkage of the mass during firing.

3. The process of making refractory compositions which consists in adding to a mix containing a hydrous oxide of aluminum suflicient'mullite to prevent the shrinkage of the mass during firing, shaping the mass and subjectin it to heat, whereby a crystalline mineral s eleton stable at elevated temperature is built up.

4. An article having the pro erties of retaining its substantial shape an volume and com osed of a major mass of a hydrous oxide of a uminum and a smaller quantity of mullite.

positions which consists in adding to a batch comprising hydrous oxide of aluminum sufli- 5. The process of making refractory com-- cient mullite to form a crystalline skeleton upon which the batch material will condense during firing of the mass.

In testimony whereof I have hereunto set my hand. Q

. LOUIS J. TROSTEL- alumina minerals-com rising diaspore, bauxite, or gibbsite, to which is added an appro pnate amount of mullite, and that one of 

